Production of colored photographic pictures



Patented Feb. 8, 1944 ITED' STATES PATENT OFFICE;

PRODUCTION OF comnno ru'oro ammo mcrouns' Bela Gaspar, Hollywood, Calii., assignor Chromogen, Incorporated, a corporation Nevada to of No Drawing. Original application September 28,

' 1941, Serial No. 412,341. Divided plication January 20, 1942, Serial No. In Great Britain December 14, 1936 and this ap- 11 Claims. (01. 95-6) In my earlier patents a process has been de scribed for the production of dyestuif images from difiusely dyed silver images. Thus, for ex-l ample, according to my 0'. S. Letters Patent 2,020,775, dated November 12, 1935, the production of such dyestufi? images is performed by Patent No. 2,020,775 and of the other dye destroying baths which were found to be applicable in the process, can be accelerated by a great number of substances other than those heretofore known. A large number of the new additions yieldtreating solutions which workrin a much more effective manner, e. g. in a much shorter time or in far smaller concentration, than the products previously proposed as accelerators.

r In view of the great eifectiveness of the additions much smaller amounts of these accelerating substances are suillcient. In many cases the presence of the accelerating compounds in the ratio of 1:100,000 is suflicient to multiply the effectiveness of the dye destroying solution.

As substances which I have found to be strong accelerators the following may be mentioned: 2 ,3-di-amino-phenazine otthe following formula:

ula:

diphen'yl-quinoxallne of the followingformula TUE Nrcl l or similar compounds of the general formula of which the formula v (II) a is a more speciflcexample. In this formula X- and Y represents groups like nitrogen, sulphur,

oxygen, carbonyl (r-=0, carbimino C=NH and the like. The compounds may be substituted by amino-groups, oxy-groups, alkyl-groups; arylgroups or other substituents including also sulphonic-groups.

Example 1 A 1% aqueous solution of hydrochloric acid which alone will not work satisfactorily on a layer diffusely colored by Diamine Fast Pink G (a dyestuif furnished by the I. G. Farbenindustrle Akt. Ges.) may be activated by the addition of Y 0.002% 2,3-diamlno-phenazlne.

" Example 2 g The action of a 2 /2% aqueous solution of hydrobromic acid. on the dyestufl Heliotrope- B (Schultz Farbstofltabellen, 1931, 1th edition; vol.

2-oxy-3-amino-phenazine of the following form- 1, No. 4941 may be considerably acceleratedby the addition of 0.002% of dianiino-phenazine. Even the addition of 7 parts of diamlno-phenazine to one million parts of a hydrobromlc acid solution'of 1.66% strength has a disflnct accele crating eflect on the local destruction of Heliotrope B. c

- Example. 3

For the production of multicolor images a multi-layer material may be used having different dyestufls incorporated in layers in which different color selection pictures are recorded. The dyestuffs may be for example Dlamlne'Pm'e Blue I"! (Schultz loc. cit. No. 510), Benzo-Light-Yellow 4 61- extra (Schultz 10c. cit-No .308) and bath mentioned in Example 4 Example 4 A solutioncontaining '10 g. thiocarbamide, 30 g. hydroguinone, 50 g. chrome alum, 5'ccm. sulphuric acid (d='l.85) per liter, with the addition of 0.2 g. 2,3-diamiuo-phenazine is used for treating exposed and developed silver halide layers containing the dyestufi obtained from diazotised ortho-anisidine and resorcinol. A dyestufi image is obtained after '7 minutes treating.

Example 5 A solution containing 74 g. potassium bromide and 17% com. sulphuric acid (11:1.84) per liter is saturated with 2,3-diphenyl-quinoxaline and then contains less than 0.01 g. per liter of this substance. The solution acts on silver images dyed with the dyestufi obtained from diazotised 4-amino-l-benzoylamino 3-methoxy-6-methylbenzol and fl-naphthol within 25 minutes or on the dvstuif obtained from diazotised o-anisidine and resorcinol within 30 minutes or on the dyestufl obtained from 'diazotised p-nitraniline and fl-naphthol within 60 minutes.

With this dyestufi and with the same treating bath the same result is obtained if, instead of the 2,3-diphenyl-quinoxaline, the 2,3-dimethylquinoxaline, the 2-oxy-3-methylquinoxaline or ordinary quinoxaline are used, 2 g. of each accelerator being used per liter. The dyestuffs chosen for the tests are in most cases insoluble azo ycstufls which in themselves are difficult to bleach out. In using dyestuffs of this sort, the differences are naturally more evident than if dyestuffs are employed which are bleached out in a shorter time in a dyestufi destroying bath without admixture. In using insoluble dyestuffs which are diflicultly bleached, the difference is so great that, for instance, the thio-carbamide which, with an adof, for instance, 2,3-'diamino-phenazine destroys the dyestuil's locally after 7 or 8 minutes of treatment, shows practically no useful efiect it the accelerating substance is omitted, even if the time of treatment is doubled.

Mention should, however, be made of the fact that the application of the admixtures has certain advantages even in the case of easily soluble and easily bleaching dyestufis, such as a shortening of the time of treatment and thereby a decrease of the detrimental effect on the layer.

The results of a large number of compounds which have been tested and found to be useful accelerators are given in the following list which shows the accelerating effect obtained by the addition of various substances to a number of treating baths used in producing dyestufi images from silver images dyed by six difierent dyestufis. These dyestufis are:

(Schultz loo. cit.

Aocchating oflect on D'yutull hydrochlodeldd 11% mod H A B, C ."i iz a -I+F+ i? I 8. Di heuyI-piperazine A B 9 DiShenyI-thiomrbozonm A:B l0 Hydrobenzamide +-ii A, B, C 11---- Methylcne-aminn-ace- +4- A,B

tonitrile. 12.--- uiuizarin. 4+;- A,Il 13---. Quinapbthalone +-ll- 4,13 14---. 2,2',4,4-tetramino-5,5'- A,B

dimethyl-diphenylmethane. 15.--- Tetrn-etlryl-p-diamino- A,B

benmphenone. 16---. Tetra-ethyl-pf-dia- B miuo-diphenyl-methane. 17.4.. Benznthio-diazol.- ++-F A, 13,0 15.". 2,1 3, dimethyl-qumo' xn- 'H-i-f- A,B

[H9- 19... 2, 3 diamino-phenazine-. ++I+ A, B, C 20.--. z-oxy'aamino- +1-H AJLC i' L phenyl) N, N'drmethyl-ethyIene-diam g ivioxetn -H A n c e v- 2L--- Am'aminm. +--l-+ ,B 24.... giscetyl-p-phenylene- A, B, 0

I'll] 25. 8djphenylethyleue-dia A,B

mine. 25.". 2, 41!iaiuinodiphenyl +++-l- A, B

amine. 27.-" Quipdizarin snlphonie +-i++ A, B

861 Zi Sodium indigo sulphon' +-l-H- A, B

ate- 29 l d-triaminobennene- +++-F A, B -iH-+ LB 30. Tegamelgldxammo- A, B, C .11.--. Tetramethyl-pdiamino- A, B, c

benmphenone. 32 Tetramethyl-p-pbenyl- A, B. C

ene-diamine hydro chloride. v 33.-.. Tetramethyl-p-diammo- A,B

diphenyl methane. ?4...-. N-methyl-qm'nolonc--. Hydmbromicocxl5% AJ! :5 N-methylfluinolone- Hydrochloric 'm-411% A, n

36 Acetone-phenylhydra- A,B

zone. 37.--- Aoetone-oxime c 38.-.. Acridone A,B 39.--- o-purine-sulphate- A, B 40. Amino-pynne A,B,C 41.... Allzmtoin. -H- A, B, c 42 Ant ne-betasul- A, B

phonic acid. 43.--. Benzalmethylamine. A, B, C 44.-.. Diacetyl-o -phenylen +-li- A, B, P Benzthiaz ylhydruine. 4.1; 46-.-. 2,chll.or-4,l'rdiamino-ben- A,B

Z0 47-.-. Sym.diphenyl-carbazide A,B 48.--. Ant one A,B, C 49---. 2,3-diphenyl-qninomline +++-i- A, B 50".. l,amino-anthmqninone-- -iH-+ A,B 51-... 2, t A,B 52.-. 1Ant m lzolg fia +-ll- AiaBc 53-..- ,me yp one Ali -s A. i 55.... Alizarine-red-Agfa +-H-+ A,B 56.-.- Di-hydro-2-hydroxyvA,B

quinoxaline. 57.--. Fuchsine A 58..-. Anthraquinone-beta- Sodium 11 rhite D sulphonic acid. (N Q Q Q 50---. etramethyl-p-diam- Accelerating eflect on 1) ino-benzophenone. hydrochlm'ic d Quinizarine sulphonic Sodium chloride 2)% E acid. plushydrocgoncadd. 61--.. --do. Magnedum chloride 1" mo e; h irochloric no: 62--.- Dimeth laminostyryl Hydrochlorlcncidll% I A, B

dimet yl-thiazo -N- ea 6 t l l d A B ,me oxy-poeu ocyanine N-ethyl-iodide. 64-.-. N-ethyl-dmethoxy-thi f A-,B

car e-iodide. 65---- N-ethyl-benzthloazol- A, B

carbocyanine-iodide.

' are especially suitable. 26, 33, 57. Furthermore, organic baseswhich group, these groups being present in anneal Accelerating eflect on Dyeltui! catalyst hydrochloric acid 11% usedr 66---. Quinone A,B,O 67--.- Benzalaniline 68...- Hexamethylenetetra- A,B

mine. 69 4.. Benzalazine A,B 70 Toluol-sulphinic acid.. C 71 enzene-l-sulphonic 3- C sulphinic acid. 72.. Naphthalene-l-sulphon- 0 ie i-sulphmic acid. 73 (3) -mtrostyryl-quinolin- A,B

' ium-N-ethyl-ethylsulphonafe. 74...- (3)-nitrostyryl-benzthi- A, B

- azol-ethyl-sulphonatc. 75".. (3)-sul ho-styrgl-pseudo- A, B

thio ydanto e. 76..-. Styryl-quinolinium- A, B

ethyl-sulphonate. -77. (4)-dimetliylamino- A,B

s l-rliodanine. 78.--. Bis 4-dimethylamino2 A,B nijtlao-phenyl) disul A, B

p l e.

=CS groups are The foregoing list of accelerating compounds embodies the results obtained with catalysts belonging to various classes of compounds. It includes, for example, reducing substances of the general type disclosed in my earlier Patent No.

2,020,775, dated November 12, 1935. In addition, the list includes-compounds of the class of re-' ducible organic substances, the reduction products of which are re-oxidizable during the treat-' ment of a dyed silver image to the original reducible substance which are claimed in my Letters Patent 2,270,118 dated January 13, 1942, of which application Serial No. 412,341, flied September 26, 1941, is a division. This application is a division of Serial No. 412,341 and the claims of the present application are directed to dye destruction baths and processes employing so-v dium hyposulphite and accelerating agents although the general listing of compounds has been set forth to indicate the comparative activity of the various accelerating compounds.

The quantityof the added catalyst was 0.2% in the experiments Nos. 1' to 5'7 and-60 to 69 oi. the list, whereas 0.8% was used in No. 58 and lysts.

also suitable in manycases. See Nos. 15, 81. Here again several of such groups may be present in'the molecule. In other cases the effective compounds are characterized by the presence of the group =C=N--, either in a ring system (No.39) or in an open chain. See Nos. 2, 3, 5, 6, ll, 36', 37, 43. Compounds of the quinone-imide type or indophenols belong to this group of catalysts. Also the compounds containing the -CN group show in many cases an acceleratingefl'ect.- A large class of accelerators is found in the class of sensitizing or desensitizing dyestuffs. See for example Nos. 62, 63, 64, 65, '73 to 77. The capacity of accelerating appears to be in no direct proportion to the sensitizing properties but on the contrary to be based mainly on the fact that these dyestuffs usually belong to one of the above-mentioned groups of accelerating substances. It may be noted that organic sulpho-compounds containing -SS, SH or ---SO2H groups are also suitable accelerators. The soluble derivatives of vat dyes are found to be also effective as cata- The tests described in the above given list of results are only examples of suitable catalysts and dyes and may be regarded as an illustration only of the new process without restriction to the dyes, catalysts or treating solutions used in the examples.

1 What I claim is:

1. In a process for producing a photographic dyestufi image in a photographic emulsion .uniformly dyed by an azo-dye and also comprising a silver image, the step of treating said silver image with a solution comprising sodium hyposulphite and a small amoun'tof anthraquinonebeta-sulphonic acid.

0.5% in No. 59. In Nos. '10 to 72 1% of the addition was used. In Nos. '73 to '7"! the quantity oi the addition was again 0.05%. In many cases far smaller quantities of the catalyst may be used for practical purposes.

As can be seen the new catalysts belong to different chemical groups. They are in most cases organic substances which can be easily hydrated or dehydrated Compounds, the re- 7 durtion-products or oxidation-products of which are capable of forming a reversible redox-system,

See, for example, Nos.

can be easily oxidized may be used. See Nos. 29, 32, 44. In many cases the bases themselves are not especially effective but can be rendered more suitable by the formation of oxidation products by auto-oxidation. The oxidation prodnets of such bases are very suitable catalysts.

the =00 group appears several times in such a compound as is the case in quinone or quinone derivatives the effectiveness is especially good. See Nos. 48, 50,. 51, 52, .58. 42, 68;

Aliphatic compounds with =80 groups or be used. See Nos.

2. In-a process for producing a photographic dyestufi image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, the step of treating said silver image with a solution of sodium hyposulphite and a small amount of a reducible organic accelerating substance selected from the group of those reducible substances, the reduction products of which are reoxidizable during the treatment of said silver image with said solution to the original reducible substance, the composition ofsaid solutionbeing such that the reduction products of said reducible. substance are reoxidizable during the treatment of said silver image and said solution being initially substantially free of reducing substances capable of being converted into said reducible substance by oxidation. I

3. A treating bath for producing a photographic dyestufi image in a photographic emulsion comprising a silver image and uniformly dyedwith an azo-dye comprising sodium hyposulphite and anthraquinone-beta-sulphonic acid.

4. In a process for producing a photographic dyestufl image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, the step of treating said silver image with a solution comprising an alkali-metal hyposulphite and a small amount of 'anthraquinonebeta-sulphonic acid. I

5. In a process of producing a dyestufl image in a photographic emulsion comprising a silver image and a uniformlydistrlbuted-azo dyestuif, the step of treating said azo dyestufi in the pres- .ence of said silver image with a solution comprising an alkali-metal hyposulphite, said treatment being carried out in the presence of a small amount of antbraquinone-beta-sulphonic acid.

6. In a process of producing a dyestufl image in a photographic emulsion comprising a silver image and a uniformly distributed azo ycstufl, the step of treating said azo dyestuit in the pres ence of said silver image with a solution comprising sodium hyposulphite, said treatment being carried out in the presence of a small amount of anthraquinone-beta-sulphonic acid.

7. In a process of producing a. photographic dyestufl' image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a metal image, the step of treating the said metal tially free of reducing substances capable of being converted into said tion. 8. In a process of producing a dyestufl image reducible substance by oxidasaid in'the presence or said silver image with a solutioncomprising sodium hyposulphite, said treatment being carried out in the presence of a quantity of a reducible organic accelerating substance suflicient to accelerate the selective destruction of said azo. dyestulf, the said accelerating substance .being selected from the group of those reducible substances, the reduction products of which are reoxidizable' during said treatment of said azo dyestufl in the presence of said silver image to the original reducible substance, said treatment with said' organic reducible accelerating substance being in the absence of reducing substances capableof being converted into said reducible substances by oiidation and the conditions of said treatment being such that the reduction products of said reducible substance are reoxidizable during said treatment in a photographic emulsion comprising a metal image and an azo dyestufi, the step of treating said azo dyestufl' in the presence of said metal 1 image with a solution comprising an alka1imetal hyposulphite, said treatment being carried out in the presence of a quantity of a reducible organic accelerating substance suflicient to accelerate the selective destruction of said azo dyestuiithe said accelerating substance being selected from the group of those reducible substances, the reduction products of which are reoxidizable during said treatment of said azo dyestufi" in the presence or said metal image to the original reducible substance, said treatment with said organic reducible accelerating substance being initiated in the absence of reducing substances capable of being converted into said reducible substances by oxidation and the conditions of saidtreatment being such that the reduction products of said reducible substance are reoxidizable during said treatment of said azo dyestuif.

9. In a process of producing a dyestufi image in a photographic emulsion comprising a silver image and an azo dyestufi, the step of treating 10. A treating bath for producing a photo graphic dyestufl. image in a photographic emulsion uniformly dyed by an azo-dye andalso oomprlsing a metal image comprising an alkali-metal hyposulphite and a small amount of a reducible .organic accelerating substance which is reducible and the reduction products of which are reoxidizable during the production of said dyestufi image to the original reducible substance, the composition of said treating bath being such that the reduction products are reoxidizable during the production of said dyestuif image and said treating bath being initially substantially free of reducing substances capable of being converted into said reducible substance by oxidation.

11. A treating bath for producing a. photographic dyestuii image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image comprising sodium hyposulphite and a small amount of a reducible organic accelerating substance which is reducible and the reduction products of which are reoxidizable during the production of said dvestuif image to the original reducible substance, the composition of said treating bath being such that the reduction products are reoxidizable during the production of said dyestufl image and said treating bath being initially substantially free of reducing substances capable of being converted into said reducible-substance by oxidation.

Bum GASPA'R T. 

